Fungicidal mixtures based on a triazolopyrimidine derivative and azoles

ABSTRACT

Disclosed are fungicidal mixtures containing A) a triazolopyrimidine derivative of formula (1), and B) an azole derivative or the salts or addition compound thereof selected among bromuconazole, difenoconazole, diniconazole, fenbuconazole, fluquinconazole, flusilazole, hexaconazole, prochloraz, tetraconazole, triflumizole, flutriafol, myclobutanil, penconazole, simeconazole, ipconazole, triticonazole, and prothioconazole as active components in a synergistically effective quantity, methods for controlling plant-pathogenic fungi by means of mixtures of compounds I and II-XVIII, substances containing said mixtures, and the use of compounds I and II-XVIII for producing such mixtures.

The present invention relates to fungicidal mixtures comprising, asactive components,

-   -   A) the triazolopyrimidine derivative of the formula I        and    -   B) an azole derivative or a salt or adduct thereof, selected        from the group consisting of        -   (1) bromuconazole of the formula II            and        -   (2) difenoconazole of the formula III            and        -   (3) diniconazole of the formula IV            and        -   (4) fenbuconazole of the formula V            and        -   (5) fluquinconazole of the formula VI            and        -   (6) flusilazole of the formula VII            and        -   (7) hexaconazole of the formula VIII            and        -   (8) prochloraz of the formula IX            and        -   (9) tetraconazole of the formula X            and        -   (10) triflumizole of the formula XI            and        -   (11) flutriafol of the formula XII            and        -   (12) myclobutanil of the formula XIII            and        -   (13) penconazole of the formula XIV            and        -   (14) simeconazole of the formula XV            and        -   (15) ipconazole of the formula XVI            and        -   (16) triticonazole of the formula XVII            and        -   (17) prothioconazole of the formula XVIII            in a synergistically effective amount.

Moreover, the invention relates to a method for controlling harmfulfungi using mixtures of the compound I with at least one of thecompounds II to XVIII and to the use of the compound I and at least oneof the compounds II to XVIII for preparing such mixtures and tocompositions comprising these mixtures.

The compound of the formula I,5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyrimidine,its preparation and its action against harmful fungi are known from theliterature (WO-A 98/46607).

Mixtures of triazolopyrimidine derivatives with other active compoundsare known in a general manner from EP-A 988 790 and U.S. Pat. No.6,268,371.

The synergistic mixtures of triazolopyrimidines described in EP-A 988790 are described as being fungicidally active against various diseasesof cereals, fruit and vegetables, in particular mildew on wheat andbarley or gray mold on apples.

The azole derivatives II to XVIII, their preparation and their actionagainst harmful fungi are known per se:

-   -   bromuconazole (II),

-   1-[4-bromo-2-(2,4-dichlorophenyl)tetrahydrofuran-2-ylmethyl]-1H-[1,2,4]triazole:    Proc. Br. Crop Prot. Conf.—Pests Dis., 5-6, 439 (1990);    -   difenoconazole (III),

-   1-{2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-[1,3]dioxolan-2-ylmethyl}-1H-[1,2,4∇triazole:    GB-A 2 098 607;    -   diniconazole (IV),

-   1-(2,4-dichlorophenyl)-4,4-dimethyl-2-[1,2,4]triazol-1-ylpent-1-en-3-ol:    CAS RN [83657-24-3];    -   fenbuconazole (V),

-   3-(4-chlorophenyl)-2-phenyl-2-[1,2,4]triazol-1-ylpropionitrile: EP-A    251 775;    -   fluquinconazole (VI),

-   3-(2,4-dichlorophenyl)-6-fluoro-2-[1,2,4]-triazol-1-yl-3H-quinazolin-4-one:    Proc. Br. Crop Prot. Conf.—Pests Dis., 5-3 (1992), 411;    -   flusilazole (VII),

-   1-{[bis(4-fluorophenyl)methylsilanyl]methyl)-1H-[1,2,4]triazole:Proc.    Br. Crop Prot. Conf.—Pests Dis., 1 (1984), 413;    -   hexaconazole (VIII),

-   2-(2,4-dichlorophenyl)-1-[1,2,4]triazol-1-ylhexan-2-ol: CAS RN    [79983-71-4];    -   prochloraz (IX),

-   N-(propyl-[2-(2,4,6-trichlorophenoxy)ethyl]}imidazole-1-carboxamide:    U.S. Pat. No. 3,991,071;    -   tetraconazole (X),

-   1-[2-(2,4-dichlorophenyl)-3-(1,1,2,2-tetrafluoroethoxy)propyl]-1H-[1,2,4]triazole:    Proc. Br. Crop Prot. Conf.-Pests Dis., 1 (1988), 49;    -   triflumizole (XI),

-   (4-chloro-2-trifluormethylphenyl)-(2-propoxy-1-[1,2,4]triazol-1-ylethylidene)amine:    JP-A 79/119 462;    -   flutriafol (XII),

-   1-(4-fluorophenyl)-1-(2-fluorophenyl)-2-[1,2,4]triazol-1-ylethanol:    CAS RN [76674-21-0];    -   myclobutanil (XIII),

-   2-(4-chlorophenyl)-2-[1,2,4]triazol-1-ylmethylpentanenitrile: CAS RN    [88671-89-0];    -   penconazole (XIV),

-   1-[2-(2,4-dichlorophenyl)pentyl]-1H-[1,2,4]triazole: Pesticide    Manual, 12th Ed. (2000), page 712;    -   simeconazole (XV),

-   1-(4-fluorophenyl)-2-[1,2,4]triazol-1-yl-1-trimethylsilanyl ethanol:    The BCPC Conference Pests and Diseases 2000, pp. 557-562;    -   ipconazole (XVI),

-   2-(4-chlorobenzyl)-5-isopropyl-1-[1,2,4]triazol-1-ylmethylcyclo    pentanol: EP-A 267 778;    -   triticonazole (XVII),

-   5-(4-chlorobenzylidene)-2,2-dimethyl-1-[1,2,4]triazol-1-ylmethyl    cyclopentanol: EP-A 378 953; and    -   prothioconazole (XVIII),

-   2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro[l,2,4]triazole-3-thione:    WO 96/16048.

Fungicidal mixtures comprising, as one active compound component, one ofthe azoles II to XVIII are known from EP-A 531 837, EP-A 645 091 and WO97/06678.

Practical agricultural experience has shown that the repeated andexclusive application of an individual active compound in the control ofharmful fungi leads in many cases to a rapid selection of fungus strainswhich have developed natural or adapted resistance against the activecompound in question. Effective control of these fungi with the activecompound in question is then no longer possible.

To reduce the risk of selection of resistant fungus strains, mixtures ofdifferent active compounds are nowadays usually employed for controllingharmful fungi. By combining active compounds having different mechanismsof action, it is possible to ensure successful control over a relativelylong period of time.

It is an object of the present invention to provide, with a view toeffective resistance management and effective control of harmful fungi,further compositions for controlling harmful fungi, in particular forcertain indications.

We have found that this object is achieved by mixtures comprising, asactive compounds, the triazolopyrimidine derivative of the formula Iand, as further fungicidally active component, an active compound fromthe group consisting of azoles II to XVIII.

Accordingly, the invention provides the mixtures defined at the outset.Moreover, it has been found that simultaneous, that is joint orseparate, application of the compounds I and the compounds II orsuccessive application of the compound I and one of the compounds II toXVIII allows better control of harmful fungi than is possible with theindividual active compounds alone.

The mixtures according to the invention act synergistically and aretherefore particularly suitable for controlling harmful fungi and inparticular powdery mildew fungi in cereals, vegetables, fruit,ornamentals and grapevines.

As azole derivative, the mixtures according to the invention comprise atleast one compound of formulae II to XVIII.

Even a small proportion of triazolopyrimidine derivative of the formulaI is sufficient for the synergistic action to take effect.Triazolopyrimidine derivative and azole are preferably employed in aweight ratio in the range from 100:1 to 1:100, preferably from 20:1 to1:20, in particular from 10:1 to 1:10.

Owing to the basic character of their nitrogen atoms, the compounds Iand II to XVIII are capable of forming salts or adducts with inorganicor organic acids or with metal ions.

Examples of inorganic acids are hydrohalic acids, such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuricacid, phosphoric acid and nitric acid. Suitable organic acids are, forexample, formic acid, carbonic acid and alkanoic acids, such as aceticacid, trifluoroacetic acid, trichloroacetic acid and propionic acid, andalso glycolic acid, thiocyanic acid, lactic acid, succinic acid, citricacid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids(sulfonic acids having straight-chain or branched alkyl radicals of 1 to20 carbon atoms), arylsulfonic or -disulfonic acids (aromatic radicals,such as phenyl and naphthyl, which carry one or two sulfonic acidgroups), alkylphosphonic acids (phosphonic acids having straight-chainor branched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic or-diphosphonic acids (aromatic radicals, such as phenyl or naphthyl,which carry one or two hosphoric acid radicals), where the alkyl or arylradicals may carry further substituents, for example p-toluenesulfonicacid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid,2-acetoxybenzoic acid, etc.

Suitable metal ions are in particular the ions of the elements of thefirst to eighth transition group, especially chromium, manganese, iron,cobalt, nickel, copper, zinc, and additionally those of the second maingroup, especially calcium and magnesium, and of the third and fourthmain group, in particular aluminum, tin and lead. If appropriate, themetals can be present in the different valencies that they can assume.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with bromuconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with difenoconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with diniconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with fenbuconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with fluquinconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with flusilazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with hexaconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with prochloraz.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with tetraconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with triflumizole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with flutriafol.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with myclobutanil.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with penconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with simeconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with ipconazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with triticonazole.

Preference is given to mixtures of the triazolopyrimidine derivative ofthe formula I with prothioconazole.

When preparing the mixtures, it is preferred to employ the pure activecompounds I and II to XVIII, to which further active compounds againstharmful fungi or other pests, such as insects, arachnids or nematodes,or else herbicidal or growth-regulating active compounds or fertilizerscan be added.

The mixtures of the compounds I and at least one of the compounds II toXVIII, or the compounds I and at least one of the compounds II to XVIIIused simultaneously, that is jointly or separately, exhibit outstandingaction against a broad spectrum of phytopathogenic fungi, in particularfrom the class of the Ascomycetes, Basidiomycetes, PhycomycetesandDeuteromycetes. Some of these compounds act systemically and cantherefore also be employed as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi onvarious crop plants, such as cotton, vegetable plants (for examplecucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass,oats, bananas, coffee, corn, fruit plants, rice, rye, soybean,grapevine, wheat, ornamentals, sugar cane and a large number of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits,Podosphaera leucotricha on apples, Uncinula necator on grapevines,Puccinia species on cereals, Rhizoctonia species on cotton, rice andgrass, Ustilago species on cereals and sugarcane, Venturia inaequalis onapples, Bipolaris and Drechslera species on cereals, rice and grass,Septoria nodorum on wheat, Botrytis cinerea on strawberries, vegetables,ornamentals and grapevines, Mycosphaerella species on bananas,groundnuts and cereals, Pseudocercosporella herpotrichoides on wheat andbarley, Pyricularia oryzae on rice, Phytophthora infestans on potatoesand tomatoes, Pseudoperonospora species on cucurbits and hops,Plasmopara viticola on grapevines, Alternaria species on vegetables andfruit, and also Fusarium and Verticillium species.

The mixtures according to the invention are preferably useful forcontrolling powdery mildew fungi in crops of cereals, grapevines andvegetables and in ornamentals.

In addition, the mixtures according to the invention are preferably alsoactive against harmful fungi from the class of Oomycetes, in particularagainst Phytophthora infestans in potatoes and tomatoes.

The mixtures according to the invention are preferably also suitable forcontrolling rice pathogens.

Owing to the special cultivation conditions of rice plants, therequirements that a rice fungicide has to meet are considerablydifferent from those that fungicides used in cereal- orfruit-cultivation have to meet. There are significant differences inmodern systems of rice culvitation: in addition to the spray applicationcustomary in many countries, in these systems the fungicide is applieddirectly onto the soil, during or shortly after sowing. The fungicide istaken up into the plant via the roots and transported in the sap of theplant to the plant parts to be protected. For rice fungicides, highsystemic action is therefore essential. In contrast, in cereal- orfruit-cultivation, the fungicide is usually applied to the leaves or thefruits; accordingly, in these crops the systemic action of the activecompounds is considerably less important.

Moreover, rice pathogens are typically different from those in cerealsor fruit. Pyricularia oryzae, Cochliobolus miyabeanus and Corticiumsasakii (syn. Rhizoctonia solani) are the pathogens of the diseases mostprevalent in rice plants. Rhizoctonia solani is the only pathogen ofagricultural significance from the sub-class Agaricomycetidae. Incontrast to most other fungi, this fungus attacks the plant not viaspores but via a mycelium infection.

For this reason, findings concerning the fungicidal activity in thecultivation of cereals or fruit cannot be transferred to rice crops.

The compound I and at least one of the compounds II to XVIII can beapplied simultaneously, that is jointly or separately, or in succession,the sequence, in the case of separate application, generally not havingany effect on the result of the control measures.

Depending on the nature of the desired effect, the application rates ofthe mixtures according to the invention are, especially in the case ofagricultural cultivation areas, from 5 to 2000 g/ha, preferably from 50to 1500 g/ha, in particular from 50 to 750 g/ha.

The application rates of the compound I here are from 1 to 1000 g/ha,preferably from 10 to 900 g/ha, in particular from 20 to 750 g/ha.

Correspondingly, the application rates of the compounds II to XVIII arefrom 1 to 1000 g/ha, preferably from 10 to 900 g/ha, in particular from20 to 750 g/ha.

In the treatment of seed, the application rates of the mixture aregenerally from 1 to 1000 g/100 kg of seed, preferably from 1 to 200g/100 kg, in particular from 5 to 100 g/100 kg.

In the control of phytopathogenic harmful fungi, the separate or jointapplication of the compounds I and at least one of the compounds II toXVIII or of the mixtures of the compounds I and at least one of thecompounds II to XVIII is carried out by spraying or dusting the seeds,the plants or the soils before or after sowing of the plants or beforeor after emergence of the plants.

The fungicidal synergistic mixtures according to the invention or thecompound I and at least one of the compounds II to XVIII can beprepared, for example, in the form of directly sprayable solutions,powder and suspensions or in the form of highly concentrated aqueous,oily or other suspensions, dispersions, emulsions, oil dispersions,pastes, dusts, compositions for broadcasting or granules, and be appliedby spraying, atomizing, dusting, broadcasting or pouring. Theapplication form depends on the particular purpose; in each case, itshould ensure fine and uniform distribution of the mixture according tothe invention.

The compounds I and II to XVIII, the mixtures or the appropriateformulations are applied by treating the harmful fungi, their habitat orthe plants, seeds, soils, areas, materials or spaces to be kept freefrom them with a fungicidally effective amount of the mixture or of thecompounds I and at least one of the compounds II to XVIII in the case ofseparate application.

Application can precede or follow infection by the harmful fungi.

The formulations are prepared in a known manner, for example byextending the active compound with solvents and/or carriers, if desiredusing emulsifiers and dispersants. Solvents/auxiliaries which aresuitable are essentially:

-   -   water, aromatic solvents (for example Solvesso products,        xylene), paraffins (for example mineral oil fractions), alcohols        (for example methanol, butanol, pentanol, benzyl alcohol),        ketones (for example cyclohexanone, gamma-butyrolactone),        pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols,        fatty acid dimethylamides, fatty acids and fatty acid esters. In        principle, solvent mixtures may also be used,    -   carriers such as ground natural minerals (for example kaolins,        clays, talc, chalk) and ground synthetic minerals (for example        finely divided silica, silicates); emulsifiers such as nonionic        and anionic emulsifiers (for example polyoxyethylene fatty        alcohol ethers, alkylsulfonates and arylsulfonates) and        dispersants such as lignin-sulfite waste liquors and        methylcellulose.

Suitable surfactants are the alkali metal, alkaline earth metal andammonium salts of lignosulfonic acid, naphthalenesulfonic acid,phenolsulfonic acid, dibutylnaphthalenesulfonic acid,alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcoholsulfates, fatty acids and sulfated fatty alcohol glycol ethers,furthermore condensates of sulfonated naphthalene and of naphthalenederivatives with formaldehyde, condensates of naphthalene or ofnaphthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,tristearylphenyl polyglycol ether, alkylaryl polyether alcohols,alcohol/- and fatty alcohol/ethylene oxide condensates, ethoxylatedcastor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene,lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfitewaste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, highly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone or water.

Powders, compositions for broadcasting and dusts can be prepared bymixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers. Examples of solid carriers are mineral earths such assilica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as, for example, ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compounds. Theactive compounds are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations: 1. Products for dilutionwith water

-   -   A) Water-soluble concentrates (SL)        -   10 parts by weight of the active compounds are dissolved in            water or in a water-soluble solvent. As an alternative,            wetters or other auxiliaries are added. The active compound            dissolves upon dilution with water.    -   B) Dispersible concentrates (DC)        -   20 parts by weight of the active compounds are dissolved in            cyclohexanone with addition of a dispersant, for example            polyvinylpyrrolidone. Dilution with water gives a            dispersion.    -   C) Emulsifiable concentrates (EC)        -   15 parts by weight of the active compounds are dissolved in            xylene with addition of calcium dodecylbenzenesulfonate and            castor oil ethoxylate (in each case 5%). Dilution with water            gives an emulsion.    -   D) Emulsions (EW, EO)        -   40 parts by weight of the active compounds are dissolved in            xylene with addition of calcium dodecylbenzenesulfonate and            castor oil ethoxylate (in each case 5%). This mixture is            introduced into water by means of an emulsifier (Ultraturax)            and made into a homogeneous emulsion. Dilution with water            gives an emulsion.    -   E) Suspensions (SC, OD)        -   In an agitated ball mill, 20 parts by weight of the active            compounds are comminuted with addition of dispersant,            wetters and water or an organic solvent to give a fine            active compound suspension. Dilution with water gives a            stable suspension of the active compound.    -   F) Water-dispersible granules and water-soluble granules (WG,        SG)        -   50 parts by weight of the active compounds are ground finely            with addition of dispersants and wetters and made into            water-dispersible or water-soluble granules by means of            technical appliances (for example extrusion, spray tower,            fluidized bed). Dilution with water gives a stable            dispersion or solution of the active compound.    -   G) Water-dispersible powders and water-soluble powders (WP, SP)        -   75 parts by weight of the active compounds are ground in a            rotor-stator mill with addition of dispersants, wetters and            silica gel. Dilution with water gives a stable dispersion or            solution of the active compound.            2. Products to be Applied Undiluted    -   H) Dustable powders (DP)        -   5 parts by weight of the active compounds are ground finely            and mixed intimately with 95% of finely divided kaolin. This            gives a dust.    -   I) Granules (GR, FG, GG, MG)        -   0.5 part by weight of the active compounds is ground finely            and associated with 95.5% carriers. Current methods are            extrusion, spray-drying or fluidized bed. This gives            granules to be applied undiluted.    -   J) ULV solutions (UL)        -   10 parts by weight of the active compounds are dissolved in            an organic solvent, for example xylene. This gives a product            to be applied undiluted.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, for example in theform of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dust, compositions forbroadcasting, or granules, by means of spraying, atomizing, dusting,broadcasting or pouring. The use forms depend entirely on the intendedpurposes; it is intended to ensure in each case the finest possibledistribution of the active compounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates suitable for dilution with water andcomposed of active substance, wetter, tackifier, dispersant oremulsifier and, if appropriate, solvent or oil.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10%, preferably from 0.01 to 1%.

The active compounds may also be used successfully in theultra-low-volume process (ULV), where it is possible to applyformulations comprising over 95% by weight of active compound, or evento apply the active compound without additives.

Oils of various type, wetters, adjuvants, herbicides, fungicides, otherpesticides, or bactericides may be added to the active compounds, ifappropriate just immediately prior to use (tank ix). These agents areusually admixed with the compositions according to the invention in aweight ratio of 1:10 to 10:1.

USE EXAMPLES

The synergistic action of the mixtures according to the invention an bedemonstrated by the experiments below:

The active compounds, separately or jointly, were prepared as a stocksolution with 0.25% by weight of active compound in acetone or DMSO. 1%by weight of the emulsifier Uniperol® EL (wetting agent havingemulsifying and dispersing action based on ethoxylated alkylphenols) wasadded to this solution. The active compounds or the mixtures werediluted with water to the stated concentration.

Evaluation was carried out by determining the infected leaf areas inpercent. These percentages were converted into efficacies. The efficacy(W) is calculated as follows using Abbot's formula:W=(1−α/β)·100

-   -   α is the level of fungicidal infection of the treated plants in        % and    -   β is the level of fungicidal infection of the untreated        (control) plants in %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of the mixtures of active compounds weredetermined using Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)]and compared with the observed efficacies.Colby's formula: E=x+y−x·y/100

-   -   E expected efficacy, expressed in % of the untreated control,        when using the mixture of the active compounds A and B at the        concentrations a and b    -   x efficacy, expressed in % of the untreated control, when using        active compound A at the concentration a    -   y efficacy, expressed in % of the untreated control, when using        active compound B at the concentration b

Use Example 1 Protective Activity against Rice Blast caused byPyricularia oryzae

Leaves of rice seedlings of the cultivar “Tai-Nong 67”, which had beengrown in pots, were sprayed to runoff point with an aqueous suspensionhaving the concentration of active compounds stated below. The next day,the plants were inoculated with an aqueous spore suspension ofPyricularia oryzae. The test plants were then placed in climatizedchambers at 22-24° C. and 95-99% relative atmospheric humidity for 6days. The extent of the development of the infection on the leaves wasthen determined visually. TABLE A Individual active compoundsConcentration of active compound Efficacy in % of in the spray theuntreated Example Active compound liquor [ppm] control 1 Control — (90%infection) (untreated) 2 I 4 33 1 11 0.25 0 3 V (fenbuconazole) 1 0 4VII (flusilazole) 1 11 5 VIII 1 11 (hexaconazole) 6 XI (triflumizole) 111 7 XVI (ipconazole) 1 11

TABLE B Mixtures according to the invention Mixture of active compoundsConcentration Observed Calculated Example Mixing ratio efficacyefficacy*) 8 I + V 67 33 4 + 1 ppm 4:1 9 I + V 56 11 1 + 1 ppm 1:1 10I + V 44 0 0.25 + 1 ppm 1:4 11 I + VII 78 41 4 + 1 ppm 4:1 12 I + VII 6721 1 + 1 ppm 1:1 13 I + VII 56 11 0.25 + 1 ppm 1:4 14 I + VIII 67 33 4 +1 ppm 4:1 15 I + VIII 67 11 1 + 1 ppm 1:1 16 I + VIII 56 0 0.25 + 1 ppm1:4 17 I + XI 67 41 4 + 1 ppm 4:1 18 I + XI 56 21 1 + 1 ppm 1:1 19 I +XI 44 11 0.25 + 1 ppm 1:4 20 I + XVI 83 41 4 + 1 ppm 4:1 21 I + XVI 6721 1 + 1 ppm 1:1 22 I + XVI 56 11 0.25 + 1 ppm 1:4*)efficacy calculated using Colby's formula

Use Example 2 Activity against Brown Spot of Rice caused by Cochliobolusmiyabeanus, Protective Treatment

Leaves of rice seedlings of the cultivar “Tai-Nong 67”, which had beengrown in pots, were sprayed to runoff point with an aqueous suspensionhaving the concentration of active compounds stated below. The next day,the plants were inoculated with an aqueous spore suspension ofCochliobolus miyabeanus. The test plants were then placed in climatizedchambers at 22-24° C. and 95-99% relative atmospheric humidity for 6days. The extent of the development of the infection on the leaves wasthen determined visually. TABLE C Individual active compoundsConcentration of active compound Efficacy in % of in the spray theuntreated Example Active compound liquor [ppm] control 23 Control — (80%Befall) (untreated) 24 I 4 33 25 II (bromuconazole) 16 50 4 25 1 13 26III 16 63 (difenoconazole) 4 38 1 13 27 IV (diniconazole) 16 25 4 0 1 028 IX (prochloraz) 16 63 4 38 1 0 29 XII (flutriafol) 16 63 4 25 1 0 30XIII 16 50 (myclobutanil) 4 0 1 0 31 XIV (penconazole) 16 63 4 25 1 0 32XVIII 16 63 (prothioconazole) 4 50 1 13

TABLE D Mixtures according to the invention Mixture of active compoundsConcentration Observed Calculated Example Mixing ratio efficacyefficacy*) 33 I + II 50 13 4 +1 ppm 4:1 34 I + II 75 25 4 + 4 ppm 1:1 35I + II 75 50 4 + 16 ppm 1:4 36 I + III 63 13 4 + 1 ppm 4:1 37 I + III 7538 4 + 4 ppm 1:1 38 I + III 94 63 4 + 16 ppm 1:4 39 I + IV 50 0 4 + 1ppm 4:1 40 I + IV 63 0 4 + 4 ppm 1:1 41 I + IV 88 25 4 + 16 ppm 1:4 42I + IX 63 0 4 + 1 ppm 4:1 43 I + IX 63 38 4 + 4 ppm 1:1 44 I + IX 88 634 + 16 ppm 1:4 45 I + XII 50 0 4 + 1 ppm 4:1 46 I + XII 63 25 4 + 4 ppm1:1 47 I + XII 88 63 4 + 16 ppm 1:4 48 I + XIII 50 0 4 + 1 ppm 4:1 49I + XIII 69 0 4 + 4 ppm 1:1 50 I + XIII 75 50 4 + 16 ppm 1:4 51 I + XIV50 0 4 + 1 ppm 4:1 52 I + XIV 63 25 4 + 4 ppm 1:1 53 I + XIV 88 63 4 +16 ppm 1:4 54 I + XVIII 63 13 4 + 1 ppm 4:1 55 I + XVIII 81 50 4 + 4 ppm1:1 56 I + XVIII 94 63 4 + 16 ppm 1:4*)efficacy calculated using Colby's formula

Use Example 3 Activity Against Peronospora of Grapevines caused byPlasmopara viticola

Leaves of potted vines were sprayed to runoff point with an aqueoussuspension having the concentration of active compound stated below. Thenext day, the undersides of the leaves were inoculated with an aqueoussporangial suspension of Plasmopara viticola. The grapevines were theninitially placed into a water-vapor-saturated chamber at 24° C. for 48hours and then placed in a greenhouse at 20-30° C. for 5 days. Afterthis period of time, the plants were again placed in a humid chamber for16 hours to promote sporangiophore eruption. The extent to which theinfection had developed on the undersides of the leaves was thendetermined visually. TABLE E Individual active compounds Concentrationof active compound in Efficacy in % of the spray liquor the untreatedExample Active compound [ppm] control 57 Control — (80% infection)(untreated) 58 I 4 38 1 0 59 VI 4 0 (fluquinconazole) 1 0 60 X(tetraconazole) 4 0 1 0 61 XVII 4 0 (triticonazole) 1 0

TABLE F Mixtures according to the invention Mixture of active compoundConcentration Observed Calculated Example Mixing ratio efficacyefficacy*) 62 I + IV 63 38 4 + 1 ppm 4:1 63 I + IV 75 38 4 + 4 ppm 1:164 I + IV 63 0 1 + 4 ppm 1:4 65 I + X 63 38 4 + 1 ppm 4:1 66 I + X 75 384 + 4 ppm 1:1 67 I + X 50 0 1 + 4 ppm 1:4 68 I + XVII 69 38 4 + 1 ppm4:1 69 I + XVII 75 38 4 + 4 ppm 1:1 70 I + XVII 50 0 1 + 4 ppm 1:4*)efficacy calculated using Colby's formula

The test results show that for all mixing ratios the observed efficacyof the mixtures according to the invention is considerably higher thanthat preducted using Colby's formula.

1. A fungicidal mixture, comprising, as active components, A) thetriazolopyrimidine derivative of the formula I

and B) an azole derivative or a salt or adduct thereof, selected fromthe group consisting of (1) bromuconazole of the formula II

and (2) difenoconazole of the formula III

and (3) diniconazole of the formula IV

and (4) fenbuconazole of the formula V

and (5) fluquinconazole of the formula VI

and (7) flusilazole of the formula VII

and (7) hexaconazole of the formula VIII

and (8) prochloraz of the formula IX

and (9) tetraconazole of the formula X

and (10) triflumizole of the formula XI

and (11) flutriafol of the formula XII

and (12) myclobutanil of the formula XIII

and (13) penconazole of the formula XIV

and (14) simeconazole of the formula XV

and (15) ipconazole of the formula XVI

and (16) triticonazole of the formula XVII

and (17) prothioconazole of the formula XVIII

in a synergistically effective amount.
 2. A fungicidal mixture asclaimed in claim 1, wherein the azole derivative is selected from thegroup consisting of (1) bromuconazole, (3) dimiconazole, (4)fenbuconazole, (5) fluquinconazole, (6) flusilazole, (8) prochloraz, (9)tetraconazole, (10) triflumizole, (11) flutriafol, (12) myclobutanil,(13) penconazole, (14) simeconazole and (17) prothioconazole.
 3. Afungicidal mixture as claimed in claim 1, wherein the azole derivativeis selected from the group consisting of (2) difenoconazole, (7)hexaconazole, (15) ipconazole and (16) triticonazole.
 4. A fungicidalmixture as claimed in claim 1, wherein the azole derivative is selectedfrom the group consisting of (13) penconazole, (14) simeconazole, (15)ipconazole, (16) triticonazole and (17) prothioconazole.
 5. A fungicidalmixture as claimed in claim 1, wherein the azole derivative is selectedfrom the group consisting of (13) penconazole, (14) simeconazole and(17) prothioconazole.
 6. A fungicidal mixture as claimed in claim 1,wherein the weight ratio of the triazolopyrimidine of the formula I tothe respective triazole of formulae II to XVIII is from 100:1 to 1:100.7. A fungicidal composition, comprising a fungicidal mixture as claimedin claim 1 and a solid or liquid carrier.
 8. A method for controllingrice-pathogenic harmful fungi, which comprises treating the harmfulfungi, their habitat or the plants, seeds, soils, areas, materials orspaces to be kept free from them with the triazolopyrimidine of theformula I as set forth in claim 1 and azoles of the formulae II to XVIIIas set forth in claim
 1. 9. A method for controlling phytopathogenicharmful fungi from the class of the Oomycetes, which comprises treatingthe harmful fungi, their habitat or the plants, seeds, soils, areas,materials or spaces to be kept free from them with thetriazolopyrimidine of the formula I as set forth in claim 1 and azolesof the formulae II to XVIII as set forth in claim
 1. 10. A method asclaimed in claim 8, wherein the compound of the formula I as set forthin claim 1 and at least one compound of formulae II to XVIII as setforth in claim 1 are applied simultaneously, that is jointly orseparately, or in succession.
 11. A method as claimed in claim 8,wherein the fungicidal mixture or the compound of the formula I and atleast one compound of formulae II to XVIII as set forth in claim 1is/are applied in an amount of from 5 to 2000 g/ha.
 12. Seed, comprisingthe mixture as claimed in claim 1 in an amount of from 1 to 1000 g/100kg.
 13. The use of the compounds I and II to XVIII as set forth in claim1 for preparing a fungicidal comosition as claimed in claim 7.